US2802877A - Preparation of omicron, omicron'-thiodiphenol - Google Patents
Preparation of omicron, omicron'-thiodiphenol Download PDFInfo
- Publication number
- US2802877A US2802877A US442187A US44218754A US2802877A US 2802877 A US2802877 A US 2802877A US 442187 A US442187 A US 442187A US 44218754 A US44218754 A US 44218754A US 2802877 A US2802877 A US 2802877A
- Authority
- US
- United States
- Prior art keywords
- thiodiphenol
- percent
- phenothioxin
- reaction mixture
- omicron
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000002360 preparation method Methods 0.000 title claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 21
- 239000011541 reaction mixture Substances 0.000 claims description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 4
- GJSGGHOYGKMUPT-UHFFFAOYSA-N phenoxathiine Chemical compound C1=CC=C2OC3=CC=CC=C3SC2=C1 GJSGGHOYGKMUPT-UHFFFAOYSA-N 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- BLDLRWQLBOJPEB-UHFFFAOYSA-N 2-(2-hydroxyphenyl)sulfanylphenol Chemical compound OC1=CC=CC=C1SC1=CC=CC=C1O BLDLRWQLBOJPEB-UHFFFAOYSA-N 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000001476 alcoholic effect Effects 0.000 description 3
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 244000286663 Ficus elastica Species 0.000 description 1
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D327/00—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms
- C07D327/02—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms one oxygen atom and one sulfur atom
- C07D327/06—Six-membered rings
- C07D327/08—[b,e]-condensed with two six-membered carbocyclic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F36/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F36/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
Definitions
- o,o'-thiodiphenol can be prepared from phenothioxin by treating the latter with an alcoholic strong alkali at elevated temperature.
- the alcoholic reaction mixture preferably contains a minor proportion of water, e. g. from about 2 to about 10 percent by weight of the reaction mixture.
- the water can be added in the form of alkali metal hydroxide containing water, or as water-containing alcohol. While the proportion of alcoholic solvent is not particularly critical, such a proportion is preferably employed that the reaction mix-- ture is a fluid liquid solution and that the concentration of alkali metal hydroxide therein at the beginning of the reaction is in the order of 20 to 40 percent by weight of the entire reaction mixture.
- the reaction is carried out at a pressure at least as great as the autogenous pressure in order to maintain the reaction mixture substantially in the liquid phase.
- the reaction can be carried out at temperatures between about and about 240 0., usually between and 240 C., and preferably between and 210 C., the time required to effect substantially complete conversion of phenothioxin to o,o'-thiodiphenol being inverse to the reaction temperature.
- the reaction can be carried out in a continuous manner, e. g. by passing the reaction mixture through an enlongated tubular reactor under reaction conditions.
- nuclearly substituted derivatives of o,o'-thiodipheno1 can be prepared from the appropriate nuclearly substituted phenothioxin.
- alkylphenothioxins, alkoxyphenothioxins and halophenothioxins can be converted to the corresponding substituted o,o'-thiodiphenols by the method of this invention.
- o,o-Thiodiphenol and related compounds are known to be useful as fungicidal and bactericidal agents (see Marsh and Butler, Ind. and Eng. Chem. 42, 839 1950) and Vietnameser et al., Z. Naturforschg. 4b, 344-50 (1949)), as stopping agents for emulsion polymerization of styrenebutadiene (see Wakefield and Bebb, Ind. and Eng. Chem. 42, 839 (1950) and Dunbrooke, India Rubber World 117, 525 1948)), and for stabilization of rubber (see U. S. Patent 2,581,930, issued January 8, 1952, to H. E. Albert).
- a method for the preparation of o,o'-thiodiphenol which comprises heating a mixture consisting essentially, by weight, of about 27 percent phenothioxin, about 30 percent potassium hydroxide, about 5 percent water and about 38 percent methanol at a temperature of about C. with agitation at autogenous pressure for about three hours, thereafter acidifying the reaction mixture and separating therefrom o,o'-thiodiphenol.
- a method for the preparation of o,o'-thiodiphenol comprises forming a reaction mixture comprising phenothioxin, an alkali metal hydroxide, water, and a lower aliphatic alcohol, the alkali metal hydroxide being present in amount corresponding to at least two mole weights per mole weight of phenothioxin and to from 20 to 40 percent by weight of the reaction mixture, and the water being present in amount corresponding to from 2 to 10 percent by weight of the reaction mixture, and heating the resulting reaction mixture at a temperature between about 125 and about 240 C. at a pressure of at least the autogenous pressure until the phenothioxin is converted substantially to o,o'-thiodiphenol.
- a method for the preparation of o,o'-thiodipheno1 which method comprises forming a reaction mixture comprising phenothioxin, potassium hydroxide, water, and methanol, the potassium hydroxide being present in amount corresponding to at least two mole weights per mole weight of phenothioxin and to from 20 to 40 percent by weight of the reaction mixture, and the water being present in amount corresponding to from 2 to 10 percent by Weight of the reaction mixture, and heating the resulting reaction mixture at a temperature between about 170 and about 210 C. at a pressure of at least the autogenous pressure until the phenothioxin is converted substantially to o,o'-thiodiphenol.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
United States PREPARATION OF 0,0-THIODIPHENOL Thomas Houtman, Midland, Mich., assignor to The Dow Chemical Company, Midland, Mich., a corporation of Delaware No Drawing. Application July 8, 1954, Serial No. 442,187
4 Claims. (Cl. 260--609) S O\ OH HO The compound herein referred to as phenothioxin is sometimes elsewhere referred to as phenoxathiin, as dibenzothioxin and as phenoxthin and can be represented by the following structural formula:
It has now been discovered that o,o'-thiodiphenol can be prepared from phenothioxin by treating the latter with an alcoholic strong alkali at elevated temperature.
A preferred procedure for practicing the invention can be illustrated by the following example.
To a solution prepared by admixing 264 gram of potassium hydroxide (having an assay of 85 percent by weight potassium hydroxide and containing about 13 percent water) and 350 mls. of methanol, there was added 200 grams of phenothioxin and the resulting mixture was enclosed in a stainless steel autoclave. The reaction mixture was heated at autogenous pressure to a tem perature of about 195 C. and was held at that temperature for about three hours, with agitation. After cooling and after being removed from the autoclave, the reaction mixture was filtered and the filtrate was acidified with concentrated hydrochloric acid, whereupon there was formed a white precipitate of o,o'-thiodiphenol. After filtering, washing and drying, there remained 200 grams of o,o'-thiodiphenol, which, when recrystallized from ethanol, melted at 139.5 to 140 C. The yield of o,o'-thiodiphenol corresponded to about 92 percent of theoretical, based on the quantity of phenothioxin taken.
The above procedure, whereby phenothioxin is converted to o,o'-thiodiphenol, can be modified. In place of all or part of the potassium hydroxide, there can be substituted another alkali metal hydroxide, e. g. sodium hydroxide. In place of all or part of the methanol, there can be substituted another lower aliphatic alcohol, e. g. ethanol. The proportions of ingredients charged to the reaction mixture can also be varied. It is preferable that an excess of alkali metal hydroxide be employed relative to the phenothioxin, i. e., at least two molecular proportions of alkali for each molecular pro- "ice portion of phenothioxin by weight. The alcoholic reaction mixture preferably contains a minor proportion of water, e. g. from about 2 to about 10 percent by weight of the reaction mixture. The water can be added in the form of alkali metal hydroxide containing water, or as water-containing alcohol. While the proportion of alcoholic solvent is not particularly critical, such a proportion is preferably employed that the reaction mix-- ture is a fluid liquid solution and that the concentration of alkali metal hydroxide therein at the beginning of the reaction is in the order of 20 to 40 percent by weight of the entire reaction mixture.
The reaction is carried out at a pressure at least as great as the autogenous pressure in order to maintain the reaction mixture substantially in the liquid phase. The reaction can be carried out at temperatures between about and about 240 0., usually between and 240 C., and preferably between and 210 C., the time required to effect substantially complete conversion of phenothioxin to o,o'-thiodiphenol being inverse to the reaction temperature.
The reaction can be carried out in a continuous manner, e. g. by passing the reaction mixture through an enlongated tubular reactor under reaction conditions.
In a manner similar to that just described, nuclearly substituted derivatives of o,o'-thiodipheno1 can be prepared from the appropriate nuclearly substituted phenothioxin. For example, alkylphenothioxins, alkoxyphenothioxins and halophenothioxins can be converted to the corresponding substituted o,o'-thiodiphenols by the method of this invention.
o,o-Thiodiphenol and related compounds are known to be useful as fungicidal and bactericidal agents (see Marsh and Butler, Ind. and Eng. Chem. 42, 839 1950) and Pfleger et al., Z. Naturforschg. 4b, 344-50 (1949)), as stopping agents for emulsion polymerization of styrenebutadiene (see Wakefield and Bebb, Ind. and Eng. Chem. 42, 839 (1950) and Dunbrooke, India Rubber World 117, 525 1948)), and for stabilization of rubber (see U. S. Patent 2,581,930, issued January 8, 1952, to H. E. Albert).
I claim:
1. A method for the preparation of o,o'-thiodiphenol which comprises heating a mixture consisting essentially, by weight, of about 27 percent phenothioxin, about 30 percent potassium hydroxide, about 5 percent water and about 38 percent methanol at a temperature of about C. with agitation at autogenous pressure for about three hours, thereafter acidifying the reaction mixture and separating therefrom o,o'-thiodiphenol.
2. A method for the preparation of o,o'-thiodiphenol, which method comprises forming a reaction mixture comprising phenothioxin, an alkali metal hydroxide, water, and a lower aliphatic alcohol, the alkali metal hydroxide being present in amount corresponding to at least two mole weights per mole weight of phenothioxin and to from 20 to 40 percent by weight of the reaction mixture, and the water being present in amount corresponding to from 2 to 10 percent by weight of the reaction mixture, and heating the resulting reaction mixture at a temperature between about 125 and about 240 C. at a pressure of at least the autogenous pressure until the phenothioxin is converted substantially to o,o'-thiodiphenol.
3. A method according to claim 2 wherein the alcohol is methanol.
4. A method for the preparation of o,o'-thiodipheno1, which method comprises forming a reaction mixture comprising phenothioxin, potassium hydroxide, water, and methanol, the potassium hydroxide being present in amount corresponding to at least two mole weights per mole weight of phenothioxin and to from 20 to 40 percent by weight of the reaction mixture, and the water being present in amount corresponding to from 2 to 10 percent by Weight of the reaction mixture, and heating the resulting reaction mixture at a temperature between about 170 and about 210 C. at a pressure of at least the autogenous pressure until the phenothioxin is converted substantially to o,o'-thiodiphenol.
4 References Cited in the file of this patent Mauthner I, Berichte 38, 1411 (1905).
Mauthner II, Berichte 39, 1350 (1906).
Hughes et al.: J. Proc. Roy Soc. N. S. Wales 83, 269 (1950), also found in Burwell, Chem. Rev. 54, 661 and 677.
Claims (1)
1. A METHOD FOR THE PREPARATION OF O,O''-THIODIPHENOL WHICH COMPRISES HEATING A MIXTURE CONSISTING ESSENTIALLY BY WEIGHT, OF ABOUT 27 PERCENT PHENOTHIOXIN, ABOUT 30 PERCENT POTASSIUM HYDROXIDE, ABOUT 5 PERCENT WATER AND ABOUT 38 PERCENT METHANOL AT A TEMPERATURE OF ABOUT 195*C. WITH AGITATION AT AUTOGENOUS PRESSURE FOR ABOUTT THREE HOURS, THEREAFTER ACIDIFYING THE REACTION MIXTURE AND SEPARATING THEREFROM O,O''-THIODIPHENOL.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US442187A US2802877A (en) | 1954-07-08 | 1954-07-08 | Preparation of omicron, omicron'-thiodiphenol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US442187A US2802877A (en) | 1954-07-08 | 1954-07-08 | Preparation of omicron, omicron'-thiodiphenol |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2802877A true US2802877A (en) | 1957-08-13 |
Family
ID=23755854
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US442187A Expired - Lifetime US2802877A (en) | 1954-07-08 | 1954-07-08 | Preparation of omicron, omicron'-thiodiphenol |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2802877A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3100229A (en) * | 1960-04-01 | 1963-08-06 | Ethyl Corp | Sulfur bridged cyclohexyl phenols |
| US3198764A (en) * | 1962-03-16 | 1965-08-03 | Dow Chemical Co | Bacteriostatic compositions of acrylonitrile polymers and 2, 2'-thiobis |
-
1954
- 1954-07-08 US US442187A patent/US2802877A/en not_active Expired - Lifetime
Non-Patent Citations (1)
| Title |
|---|
| None * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3100229A (en) * | 1960-04-01 | 1963-08-06 | Ethyl Corp | Sulfur bridged cyclohexyl phenols |
| US3198764A (en) * | 1962-03-16 | 1965-08-03 | Dow Chemical Co | Bacteriostatic compositions of acrylonitrile polymers and 2, 2'-thiobis |
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